Influence of adsorbed polar molecules on the electronic transport in a composite material Li1.1V3O8–PMMA for lithium batteries

Abstract

The broadband dielectric spectroscopy (BDS) technique (40 to 10¹⁰ Hz) is used here to measure the electronic transport across all observed size scales of a Li_1.1V₃O₈–polymer-gel composite material for lithium batteries. Different electrical relaxations are evidenced, resulting from the polarizations at the different scales of the architecture: (i) atomic lattice (small-polaron hopping), (ii) particles, (iii) clusters of particles, and finally (iv) sample–current collector interface. A very good agreement with dc-conductivity measurements on a single macro-crystal [M. Onoda and I. Amemiya, J. Phys.: Condens. Matter, 2003, 15, 3079.] shows that the BDS technique does allow probing the bulk (intrinsic) electrical properties of a material in the form of a network of particles separated by boundaries in a composite. Moreover, this study highlights a lowering of the surface electronic conductivity of Li_1.1V₃O₈ particles upon adsorption of polar ethylene carbonate (EC) and propylene carbonate (PC) that trap surface polarons. This result is meaningful as EC and PC are typical constituents of a liquid electrolyte of lithium batteries. It is thus suggested that interactions between active material particles and the liquid electrolyte play a role in the electronic transport within composite electrodes used in a lithium battery.